Water insoluble alpha-(1,3-glucan) composition

ABSTRACT

The disclosure relates to a coating composition that can be applied to a substrate, especially a cellulose substrate. A layer of the coating composition applied to the substrate provides an excellent ink receptive layer and can be used as a coating on paper. The disclosure also relates to aqueous compositions and method for applying the layer of the coating composition onto the substrate.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority of U.S. ProvisionalApplication No. 62/246,308, filed on Oct. 26, 2015; the entiredisclosure of which is hereby incorporated by reference.

FIELD OF THE DISCLOSURE

The present disclosure is directed towards compositions comprising waterinsoluble α-(1,3→glucan) polymer and its use as an ink receiving layerfor paper, plastic, and textiles. The use of the water insolubleα-(1,3→glucan) polymer produces fast-drying surfaces that provide sharpimages that show very little bleeding or mottling after having beenprinted with ink from a printer, for example, ink jet printing.

BACKGROUND OF THE DISCLOSURE

The paper industry produces many different kinds of paper, dependingupon its ultimate use. In many cases, the uncoated paper does not havesufficient properties to allow printing directly to the surface. Forthis reason, paper is often coated with one or more layers in order torender the surface receptive to inks. The coatings are generally madefrom starch, a thermoplastic polymer, a non-thermoplastic polymer or acombination thereof. Starch, however, tends to form a gelatinous slurrywhich can be difficult to work with and thermoplastics can be expensiveand are not easily recyclable when applied to paper.

There are many requirements for an ink receiving layer, not only forpaper, but for any printable surface, for example, plastic sheets andtextiles. The ink receiving layer should have a high ink absorbingcapacity, so that the dots will not flow out and will not be expandedmore than is necessary to obtain a high optical density, even if inkdroplet in a multi-color system may be superposed on the same physicalspot. The ink receiving layer should have a high ink absorbing speed(short ink drying time) so that the ink droplets will not feather ifsmeared immediately after applying. The ink receiving layer should beexcellent in color forming characteristics. The ink receiving layer mustbe readily wetted so that there is no “puddling”, i.e. coalescence ofadjacent ink dots, and an earlier absorbed ink drop should not show any“bleeding”, i.e. overlap with neighboring or later placed dots. It musthave a low haze-value and be excellent in transmittance properties.

After being printed, the image must have a good resistance to water,light, and/or time-dependent discoloration. The ink recording elementmay not show any curl or sticky behavior if stacked before or afterbeing printed.

To meet these requirements, the ink receptive layers of the prior arthave been prepared using many different materials. A dimensionallystable substrate such as polyethylene terephtalate (PET), cellulosetriacetate, or paper is used most frequently and coated with one or morepolymer coatings. There is a need for an ink receiving layer that can becoated onto multiple substrates and provide all of the properties thatare needed for such a layer.

SUMMARY OF THE DISCLOSURE

The disclosure relates to a substrate, wherein at least a portion of thesubstrate is coated with a layer of a coating composition, the coatingcomposition comprising;

-   -   i) water insoluble α-(1,3→glucan) polymer having 90% or greater        α-1,3-glycosidic linkages, less than 1% by weight of        α-1,3,6-glycosidic branch points and a number average degree of        polymerization in the range of from 55 to 10,000; and    -   ii) at least one pigment, at least one binder or a combination        thereof.

In other embodiments, the disclosure relates to a method of forming alayer of a coating composition on a substrate comprising:

-   -   1) applying an aqueous coating composition to at least a portion        of a substrate, wherein the aqueous coating composition        comprises;    -   i) water insoluble α-(1,3→glucan) polymer having 90% or greater        α-1,3-glycosidic linkages, less than 1% of α-1,3,6-glycosidic        branch points and a number average degree of polymerization in        the range of from 55 to 10,000;    -   ii) a pigment, a binder or a combination thereof;    -   iii) an aqueous carrier; and    -   2) removing at least a portion of the aqueous carrier from the        applied layer of the aqueous coating composition to form the        layer of the coating composition.

The disclosure further relates to the aqueous coating composition.

DETAILED DESCRIPTION OF THE DISCLOSURE

The disclosures of all cited patent and non-patent literature areincorporated herein by reference in their entirety.

As used herein, the term “embodiment” or “disclosure” is not meant to belimiting, but applies generally to any of the embodiments defined in theclaims or described herein. These terms are used interchangeably herein.

Unless otherwise disclosed, the terms “a” and “an” as used herein areintended to encompass one or more (i.e., at least one) of a referencedfeature.

The features and advantages of the present disclosure will be morereadily understood by those of ordinary skill in the art from readingthe following detailed description. It is to be appreciated that certainfeatures of the disclosure, which are, for clarity, described above andbelow in the context of separate embodiments, may also be provided incombination in a single element. Conversely, various features of thedisclosure that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any sub-combination.In addition, references to the singular may also include the plural (forexample, “a” and “an” may refer to one or more) unless the contextspecifically states otherwise.

The use of numerical values in the various ranges specified in thisapplication, unless expressly indicated otherwise, are stated asapproximations as though the minimum and maximum values within thestated ranges were both proceeded by the word “about”. In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding each and every value between the minimum and maximum values.

As used herein:

The term “starch” means a polymeric carbohydrate consisting of amyloseand amylopectin.

The term “hydroxyalkyl starch” means an ether derivative of partiallyhydrolyzed natural starches, in which hydroxyl groups in the starch arehydroxyl alkylated.

The phrase “water insoluble” means that less than 5 grams of theα-(1,3→glucan) polymer dissolves in 100 milliliters of water at 23° C.In other embodiments, water insoluble means that less than 4 grams or 3grams or 2 grams or 1 grams of the polymer is dissolved in water at 23°C.

The phrase “α-(1,3→glucan) polymer” means a polysaccharide comprisingglucose monomer units linked together by glycosidic linkages wherein atleast 50% of the glycosidic linkages are α-1,3-glycosidic linkages. Inother embodiments, the percentage of α-1,3-glycosidic linkages can begreater than or equal to 90%, 95%, 96%, 97%, 98%, 99% or 100% (or anyinteger value between 50% and 100%). Accordingly, the α-(1,3→glucan)polymer comprises less than or equal to 10%, 5%, 4%, 3%, 2%, 1% or 0% ofglycosidic linkages that are not α-1,3-glycosidic linkages.

The terms “glycosidic linkage” refers to the type of covalent bond thatjoins a carbohydrate (sugar) molecule to another group such as anothercarbohydrate. The term “alpha-1,3-glycosidic linkage” as used hereinrefers to the type of covalent bond that joins alpha-D-glucose moleculesto each other through carbons 1 and 3 on adjacent alpha-D-glucose rings.Herein, “alpha-D-glucose” will be referred to as “glucose”.

The phrase “coating composition” refers to all of the solid componentsthat form the layer on the substrate, for example, the α-(1,3→glucan)polymer, pigment, as well as optional surfactant, dispersing agent,binder, crosslinking agent, and/or other additives. The term solid isused even though some of the components may be liquids at or below roomtemperature.

The phrase “aqueous coating composition” refers to the coatingcomposition further comprising an aqueous carrier. After being appliedto a substrate, at least a portion of the aqueous carrier is removed toform the desired layer of the coating composition on the substrate.Removing at least a portion of the aqueous carrier means to removegreater than or equal to 50% by weight of the aqueous carrier. In otherembodiments, greater than or equal to 90% or 95% or 99% by weight of theaqueous carrier is removed. Water content can be assessed by KarlFischer titration.

The phrase “consists essentially of” means that the composition containsall of the recited components and less than 5% by weight, based on thetotal weight of the composition of any other component or combination ofcomponents. For example, a composition consisting essentially of A and Bmust contain at least 95% by weight of A and B and no more than 5% byweight of any other component or combination components, wherein thepercentage by weight is based on the total weight of the composition. Inother embodiments, the phrase consisting essentially of means that thecomposition contains less than 4% or 3% or 2% or 1% or less than 0.5% byweight of the components that are not recited, based on the total weightof the composition.

In some embodiments, the present disclosure relates to a substrate,wherein at least a portion of the substrate is coated with a layer of acoating composition, the coating composition comprising:

-   -   i) water insoluble α-(1,3→glucan) polymer having 90% or greater        α-1,3-glycosidic linkages, less than 1% of α-1,3,6-glycosidic        branch points and a number average degree of polymerization in        the range of from 55 to 10,000; and    -   ii) a pigment, a binder or a combination thereof.

The present disclosure also relates to a method of forming a layer of acoating composition on a substrate comprising:

-   -   1) applying a layer of an aqueous coating composition to at        least a portion of a substrate, wherein the aqueous coating        composition comprises;        -   i) water insoluble α-(1,3→glucan) polymer having 90% or            greater α-1,3-glycosidic linkages, less than 1% of            α-1,3,6-glycosidic branch points and a number average degree            of polymerization in the range of from 55 to 10,000;        -   ii) a pigment, a binder or a combination thereof; and        -   iii) an aqueous carrier; and    -   2) removing at least a portion of the aqueous carrier from the        applied layer of the aqueous coating composition to form the        layer of the coating composition.

The water insoluble α-(1,3→glucan) polymer can be produced using anenzymatic method, for example, a method using glucosyl transferaseenzymes as provided by U.S. Pat. No. 7,000,000 or U.S. Pat. No.8,871,474. In some embodiments, the water insoluble α-(1,3→glucan)polymer is produced by a glucosyltransferase enzyme having 90% orgreater sequence identity to Gtf J. An enzymatic production of the waterinsoluble α-(1,3→glucan) polymer can result in a number average degreeof polymerization (DPn) in the range of from 55 to 10,000. In otherembodiments, the DPn can be in the range of from 75 to 1,000 and, instill further embodiments, in the range of from 100 to 800. The numberaverage degree of polymerization can be determined by size exclusionchromatography.

The enzymes disclosed in the above references are also particularlyuseful for producing water insoluble fiber having greater than or equalto 90% α-1,3-glycosidic linkages. The water insoluble α-(1,3→glucan)polymer comprising greater than or equal to 90% α-1,3-glycosidiclinkages is herein to be considered a linear polymer having ahomogeneous structure. By homogeneous structure is meant that the waterinsoluble α-(1,3→glucan) polymer has less than 10% linkages that are notα-1,3-glycosidic linkages, for example, α-1,6-glycosidic linkagesα-1,4-glycosidic linkages or α-1,3,6-glycosidic branch points. In otherembodiments, the water insoluble α-(1,3→glucan) polymer comprises lessthan 9% or 8% or 7% or 6% or 5% or 4% or 3% or 2% or 1% of glycosidiclinkages that are not α-1,3-linkages. In still further embodiments, thewater insoluble α-(1,3→glucan) polymer is a linear polymer havinggreater than or equal to 99% of α-1,3-glycosidic linkages and less than1% α-1,3,6-glycosidic branch points. As used herein the percentage ofα-1,3-glycosidic linkages refers to the average number of monomer unitsthat are linked via α-1,3-linkages divided by the total number ofmonomer units in the polymer composition (×100). The percentage ofα-1,3-glycosidic linkages is determined via integration of the peaks ina ¹H NMR spectra, wherein a sample of the water insoluble α-(1,3→glucan)polymer is solvated in d₆-dimethyl sulfoxide (DMSO) containing 3 percentby weight LiCl and 0.1 milliliters of trifluoroacetic acid in d₆-DMSO.The percentages of linkages that are not α-1,3-glycosidic linkages canbe determined in the same manner and using the same general formula.

It is important that the α-(1,3→glucan) polymer is water insoluble. Theaqueous coating composition that is applied to the substrate is adispersion of the water insoluble α-(1,3→glucan) polymer in water. Whenapplied to at least a portion of the substrate and the applied layer isdried, the layer of coating composition comprises an average pore sizevolume in the range of from 0.1 to 0.50 milliliters/gram (ml/g), asmeasured by mercury porosimetry. In other embodiments, the average poresize volume can be in the range of from 0.12 to 0.45 or 0.14 to 0.40ml/g. In contrast, a water soluble polysaccharide composition, whenapplied to a substrate, forms a continuous layer that does not havepores or voids on the same scale as the water insoluble α-(1,3→glucan)polymer. The phrase “discontinuous layer” means a layer with individualparticles wherein a free standing layer of the material has anelongation to break of less than 5%.

The water insoluble α-(1,3→glucan) polymer can comprise in the range offrom 0.1% to about 50% by weight based on the total amount of thecoating composition. In other embodiments, the water insolubleα-(1,3→glucan) polymer can comprise in the range of from 1% to 45% or 2%to 40% or 3% to 35% or 3% to 30% by weight of the water insolubleα-(1,3→glucan) polymer, wherein all percentages by weight are based onthe total weight of the coating composition.

The coating composition also comprises at least one pigment, at leastone binder, or a combination thereof. In some embodiments, the coatingcomposition comprises the water insoluble α-(1,3→glucan) polymer and apigment. In some embodiments, the coating composition consistsessentially of the water insoluble α-(1,3→glucan) polymer and a pigment.In some embodiments, the coating composition comprises the waterinsoluble α-(1,3→glucan) polymer and a binder. In other embodiments, thecoating composition consists essentially of the water insolubleα-(1,3→glucan) polymer and a binder. In some embodiments, the coatingcomposition comprises the water insoluble α-(1,3→glucan) polymer, apigment, and a binder. In other embodiments, the coating compositionconsists essentially of the water insoluble α-(1,3→glucan) polymer, apigment, and a binder.

The coating composition can comprise the water insoluble α-(1,3→glucan)polymer and a pigment. One or more pigments can be included in thecoating compositions. Suitable pigments can include, for example,titanium dioxide, calcium carbonate, clays such as kaolin, structuredand calcined clays, hydrated aluminum silicates, bentonite, natural andsynthetic calcium carbonate, calcium sulphate (gypsum), calciumsilicate, calcium silicate hydrate, silicas, precipitated silicas, fumedsilicas, alumina, aluminum trihydrate, plastic (polystyrene) pigments,satin white, talc, barium sulphate, zinc oxide, or a combinationthereof. In some embodiments, the pigment is calcium carbonate,crystalline silica, amorphous silica, titanium dioxide calcium silicate,or a combination thereof. The pigment can be present in the range offrom 10 to 75% by weight, based on the total weight of the coatingcomposition. In other embodiments, the pigment can be present in therange of from 20 to 70% by weight or 25 to 65% by weight, based on thetotal weight of the coating composition.

The coating composition can comprise the water insoluble α-(1,3→glucan)polymer and a binder. The binder can comprise in the range of from 1 to50% by weight of the coating composition, based on the total weight ofthe coating composition. In other embodiments, the binder can comprisein the range of from 2 to 45% or 2 to 40% or 2 to 30% by weight of thecoating composition, wherein the percentages by weight are based on thetotal weight of the coating composition. One or more binders can beincluded in the coating compositions. Suitable binders can include, forexample, polyvinyl alcohol, polyvinyl acetate, partially saponifiedpolyvinyl acetate, silanol-modified polyvinyl alcohol, polyurethane,starch, corn dextrin, carboxy methyl cellulose, cellulose ethers,hydroxyethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethylcellulose, methyl cellulose, alginates, sodium alginate, xanthan,carrageenan, casein, soy protein, guar gums, synthetic polymers, styrenebutadiene latex, styrene acrylate latex, or a combination thereof. Insome embodiments, the binder is polyvinyl alcohol, polyvinyl acetate,partially saponified polyvinyl acetate, silanol-modified polyvinylalcohol, polyurethane, starch, corn dextrin, cellulose ethers,hydroxyethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethylcellulose, methyl cellulose, alginates, sodium alginate, xanthan,carrageenan, guar gums, synthetic polymers, styrene butadiene latex, ora combination thereof. In some embodiments, the binder is polyvinylalcohol. In other embodiments, the binder is a combination of two ormore of polyvinyl alcohol, a silanol-modified polyvinyl alcohol andpolyvinyl acetate. If present, the coating composition can comprise upto 50% by weight of the binder, wherein the percentage by weight isbased on the total amount of the coating composition. In someembodiments, the coating composition is free from the binder. In otherembodiments, the coating composition is free from starch and/orhydroxyalkyl starch. In other embodiments, the coating composition isfree from water soluble polysaccharides. As used herein, the phrase freefrom means that the coating composition contains less than 1% by weightof the component, or less than 0.5% by weight or less than 0.1% byweight or less than 0.01% by weight of the component. In still furtherembodiments, free from means that the particular component isundetectable by ¹H NMR.

The coating composition can further comprise iv) an additive. One ormore of each of these components can be added. For example, theadditives category encompasses a large number of potential components ofwhich one or more of the individual components can be used. In someembodiments, a pigment and/or a binder, and one or more additives can beused. In other embodiments, the coating composition can include apigment and one or more additives without the addition of a binder. Instill further embodiments, the coating composition can include a binderand one or more additives without the addition of a pigment.

The coating composition can further comprise any of the additives thatare normally used in paper coatings. Suitable additives can include, forexample, dispersants, quaternary ammonium salts, calcium chloride,calcium silicate; surfactants, for example, cationic surfactants,anionic surfactants, non-ionic surfactants, amphoteric surfactants,fluorinated surfactants; hardeners, for example, active halogencompounds, vinylsulfone compounds, epoxy compounds; dispersing agents,for example, polyacrylates, polyphosphates, polycarboxylates,flowability improvers; lubricants, for example, calcium, ammonium and/orzinc stearate, wax or wax emulsions, alkyl ketene dimer, glycols;antifoam agent, for example, octyl alcohol, silicone-based antifoamagents; releasing agents; foaming agents; penetrants, for example,1,2-propanediol, triethylene glycol butyl ether, 2-pyrrolidone; opticalbrighteners, for example, fluorescent whiteners; preservatives, forexample, benzoisothiazolone and isothiazolone compounds; biocides, forexample, metaborate, thiocyanate, sodium benzoate,benzisothiaolin-3-one; yellowing inhibitors, for example, sodiumhydroxymethyl sulfonate, sodium p-toluenesulfonate; ultravioletabsorbers, for example, benzotriazole compounds; antioxidants, forexample, sterically hindered phenol compounds; insolubilisers;antistatic agents; pH regulators, for example, weak bases, primary,secondary or tertiary amines, sulfuric acid, hydrochloric acid;water-resistance agents, for example, ketone resin, anionic latex,glyoxal; wet and/or dry strengthening agents, for example, glyoxal-basedresins, oxidized polyethylenes, melamine resins, urea formaldehyde;cross-linking agents; gloss-ink holdout additives; grease and oilresistance additives; leveling aids, for example, polyethyleneemulsions, alcohol/ethylene oxide or combinations thereof. In someembodiments, the coating composition further comprises one or more of anadditive, wherein the additive is one or more of a dispersant, aquaternary ammonium salts, calcium chloride, a surfactant, a hardener, aflowability improver, a lubricant, an antifoam, a releasing agent, afoaming agent, a penetrant, an optical brightener, a preservative, abiocide, a yellowing inhibitor, an ultraviolet absorber, an antioxidant,an insolubiliser, an antistatic agent, a pH regulator, awater-resistance agent, a wet and/or dry strengthening agent, across-linking agent, a gloss-ink holdout additive, a grease and oilresistance additive, a leveling aid, or a combination thereof. Thecoating composition can contain any one or more of the listed additivesin an amount in the range of from 0 to 5% by weight, based on the totalamount of the coating composition. In other embodiments, the additivescan be present in an amount in the range of from 0.1 to 4% by weight or0.5 to 3.5% by weight or 0.5 to 3% by weight. All percentages by weightare based on the total amount of the coating composition.

The individual components of the coating composition can be dispersed inan aqueous carrier to form the aqueous coating composition. As usedherein, aqueous carrier means a liquid carrier comprising greater thanor equal to 50% by weight of water. In other embodiments, the aqueouscarrier comprises greater than or equal to 75% or 85% or 90% or 95%water, all percentages by weight are based on the total amount of theaqueous carrier. Volatile non-aqueous solvents may be present, forexample alcohols or other organic solvents, however, it is expected thatthe amount of the non-aqueous carriers will be low when compared to theamount of water present in the aqueous coating composition. The amountof aqueous carrier in the aqueous coating composition less than or equalto 95% by weight, based on the total weight of the aqueous coatingcomposition. In other embodiments, the aqueous carrier is present atless than or equal to 90% or 85% or 80% or 75% or 70% or 65% or 60% or55% or 50% or 40% or 30% or 20% by weight, based on the total weight ofthe aqueous coating composition. In general, the aqueous coatingcomposition should have a viscosity that allows a relatively smoothcoating to be applied to the surface of the substrate without lumps,voids, or streaking. Such application details are well-known to one ofordinary skill in the art.

The aqueous coating composition can be formed using standard methodsknown in the art. For example, the dry ingredients can be added to watereither all at once, in batches, or one after the other. For example,pigments, with any additives, can be mixed with the aqueous carrierfirst, followed by the addition of the water insoluble α-(1,3→glucan)polymer as a powder or as a wet cake. In other embodiments, thecomponents of the coating composition can be dry-blended to form apre-mix which can then be added to the aqueous carrier. The aqueouscoating composition should be mixed thoroughly, in order to form adispersion of the water-insoluble α-(1,3→glucan) polymer.

The present disclosure also relates to a method of forming a layer of acoating composition on a substrate comprising:

-   -   1) applying a layer of an aqueous coating composition to at        least a portion of a substrate, wherein the aqueous coating        composition comprises;        -   i) water insoluble α-(1,3→glucan) polymer having 90% or            greater α-1,3-glycosidic linkages, less than 1% of            α-1,3,6-glycosidic branch points and a number average degree            of polymerization in the range of from 55 to 10,000;        -   ii) a pigment, a binder or a combination thereof; and an            aqueous carrier; and    -   2) removing at least a portion of the aqueous carrier from the        applied layer of the aqueous coating composition to form the        layer of the coating composition.

The step of applying the layer of the aqueous coating composition to atleast a portion of the substrate can be accomplished by any means knownin the art. The substrate can be a cellulose substrate, a polymer,paper, a textile, paperboard, cardboard, or corrugated board. In someembodiments, the polymer substrate can be a transparency sheet, forexample comprising cellulose acetate, polyester, or polyvinyl chloride.

Methods of applying the layer of the aqueous coating composition caninclude, for example, air knife coating, rod coating, bar coating, wirebar coating, spray coating, brush coating, cast coating, flexible bladecoating, gravure coating, jet applicator coating, short dwell coating,slide hopper coating, curtain coating, flexographic coating, size-presscoating, reverse roll coating and transfer roll coating. The aqueouscoating composition can be applied on at least a portion of thesubstrate, for example, on a single side or both sides of the substrate,a portion of a single side, or a portion of both sides of a flatsubstrate. The aqueous coating can be applied once to the substrate ormultiple times to the substrate.

In other embodiments, the aqueous coating composition can be applied tothe substrate either shortly before or during the printing operation.For example, a printing machine such as an ink jet printer, may beequipped to apply a layer of the aqueous coating composition to aportion of the paper that will receive the ink prior to placing the inkon the substrate. The layer of coating composition applied in thismanner can be the same size as the to-be-applied ink or can be largerthan the to-be-applied ink.

After the coating step, at least a portion of the water is removed byany method known in the art. For example, air or convection drying,linear tunnel drying, arc drying, air-loop drying, contact or conductiondrying, radiant energy drying, infrared drying, microwave drying, or acombination thereof may be used. The coated substrate can optionally becalendared after drying in order to improve the surface smoothness andgloss. Calendaring can be carried out by passing the coated substratethrough nips and rollers one or more times.

The aqueous coating composition can be applied to the substrate at sucha rate as to apply a dry coating weigh in the range of from 0.1 to 30grams/meter² (g/m²). In other embodiments, the dry coating weight can bein the range of from 0.5 to 25 g/m² or 1 to 20 g/m². The applied layerof coating composition can have a thickness in the range of from 0.1 to50 micrometers (μm). In other embodiments, the thickness can be in therange of from 0.5 to 40 μm or 1 to 30 μm or 1 to 20 μm.

Non-limiting examples of the embodiments disclosed herein include:

1. A substrate, wherein at least a portion of the substrate is coatedwith a layer of a coating composition, the coating compositioncomprising;

-   -   i) water insoluble α-(1,3→glucan) polymer having 90% or greater        α-1,3-glycosidic linkages, less than 1% by weight of        α-1,3,6-glycosidic branch points and a number average degree of        polymerization in the range of from 55 to 10,000; and    -   ii) at least one pigment, at least one binder or a combination        thereof.        2. The substrate of embodiment 1 wherein the substrate is a        cellulose substrate, a polymer, paper, a textile, paperboard,        cardboard, or corrugated board.        3. The substrate of any one of embodiments 1 or 2 wherein the        layer of coating composition comprises an average pore size        diameter in the range of from 0.10 to 0.50 milliliters/gram.        4. The substrate of any one of embodiments 1, 2 or 3 wherein the        binder is polyvinyl alcohol, polyvinyl acetate, partially        saponified polyvinyl acetate, silanol-modified polyvinyl        alcohol, polyurethane, starch, corn dextrin, carboxy methyl        cellulose, cellulose ethers, hydroxyethyl cellulose,        hydroxypropyl cellulose, ethylhydroxyethyl cellulose, methyl        cellulose, alginates, sodium alginate, xanthan, carrageenan,        casein, soy protein, guar gums, synthetic polymers, styrene        butadiene latex, styrene acrylate latex, or a combination        thereof.        5. The substrate of any one of embodiments 1, 2, 3 or 4 wherein        the coating composition comprises in the range of from 0.1 to        50% by weight of the water insoluble α-(1,3→glucan) polymer,        wherein the percentage by weight is based on the total weight of        the coating composition.        6. The substrate of any one of embodiments 1, 2, 3, 4 or 5        wherein the coating composition further comprises one or more        of:    -   iv) an additive.        7. The substrate of claim 1 wherein the water insoluble        α-(1,3→glucan) polymer is a linear polymer having greater than        or equal to 99% of α-1,3-glycosidic linkages and less than 1%        α-1,3,6-glycosidic branch points.        8. The substrate of any one of embodiments 1, 2, 3, 4, 5 or 6        wherein the coating composition is free from or essentially free        from starch and/or hydroxyalkyl starch.        9. The substrate of any one of embodiments 1, 2, 3, 4, 5, 6, 7        or 8 wherein the binder is polyvinyl alcohol, polyvinyl acetate,        partially saponified polyvinyl acetate, silanol-modified        polyvinyl alcohol, polyurethane, starch, corn dextrin, cellulose        ethers, hydroxyethyl cellulose, hydroxypropyl cellulose,        ethylhydroxyethyl cellulose, methyl cellulose, alginates, sodium        alginate, xanthan, carrageenan, guar gums, synthetic polymers,        styrene butadiene latex or a combination thereof.        10. The substrate of any one of embodiments 6, 7 8 or 9 wherein        the additive is one or more of a dispersant, a quaternary        ammonium salts, calcium chloride, a surfactant, a hardener, a        flowability improver, a lubricant, an antifoam, a releasing        agent, a foaming agent, a penetrant, an optical brightener, a        preservative, a biocide, a yellowing inhibitor, an ultraviolet        absorber, an antioxidant, an insolubiliser, an antistatic agent,        a pH regulator, a water-resistance agent, a wet and/or dry        strengthening agent, a cross-linking agent, a gloss-ink holdout        additive, a grease and oil resistance additive, a leveling aid,        or a combination thereof.        11. An aqueous coating composition comprising the coating        composition of any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9        or 10 and        iii) an aqueous carrier.        12. The aqueous coating composition of embodiment 11 wherein the        α-(1,3→glucan) polymer is produced by a glucosyltransferase        enzyme having 90% or greater sequence identity to Gtf J.        13. The aqueous coating composition of any one of embodiments 11        or 12 wherein the aqueous coating composition is free from water        soluble polysaccharides.        14. The aqueous coating composition of any one of embodiments        11, 12 or 13 wherein the aqueous carrier comprises less than or        equal to 60% by weight of the total weight of the aqueous        coating composition.        15. The aqueous coating composition of any one of embodiments        11, 12, 13 or 14 wherein the composition further comprises one        or more of:    -   iv) an additive.        16. The aqueous coating composition of any one of embodiments        11, 12, 13, 14 or 15 wherein the composition is essentially free        from starch and/or hydroxyalkyl starch.        17. The aqueous coating composition of any one of embodiments        11, 12, 13,1 4, 15 or 16 wherein the α-(1,3→glucan) polymer is a        linear polymer having greater than or equal to 99% of        α-1,3-glucosydic linkages and less than 1% α-1,3,6-branching        points.        18. The aqueous coating composition of any one of embodiments        11, 12, 13, 14, 15, 16 or 17 wherein the binder is polyvinyl        alcohol, polyvinyl acetate, partially saponified polyvinyl        acetate, silanol-modified polyvinyl alcohol, polyurethane,        starch, corn dextrin, cellulose ethers, hydroxyethyl cellulose,        hydroxypropyl cellulose, ethylhydroxyethyl cellulose, methyl        cellulose, alginates, sodium alginate, xanthan, carrageenan,        guar gums, synthetic polymers, styrene butadiene latex or a        combination thereof.        19. The aqueous composition of any one of embodiments 15, 16, 17        or 18 wherein the additive is one or more of a dispersant, a        quaternary ammonium salts, calcium chloride, a surfactant, a        hardener, a flowability improver, a lubricant, an antifoam, a        releasing agent, a foaming agent, a penetrant, an optical        brightener, a preservative, a biocide, a yellowing inhibitor, an        ultraviolet absorber, an antioxidant, an insolubiliser, an        antistatic agent, a pH regulator, a water-resistance agent, a        wet and/or dry strengthening agent, a cross-linking agent, a        gloss-ink holdout additive, a grease and oil resistance        additive, a leveling aid or a combination thereof.        20. A method of forming a layer of a coating composition on a        substrate comprising:    -   1) applying an aqueous coating composition to at least a portion        of a substrate, wherein the aqueous coating composition        comprises;        -   i) water insoluble α-(1,3→glucan) polymer having 90% or            greater α-1,3-glycosidic linkages, less than 1% of            α-1,3,6-glycosidic branch points and a number average degree            of polymerization in the range of from 55 to 10,000;        -   ii) a pigment, a binder or a combination thereof;        -   iii) an aqueous carrier; and    -   2) removing at least a portion of the aqueous carrier from the        applied layer of the aqueous coating composition to form the        layer of the coating composition.        21. The method of embodiment 20 wherein the a) α-(1,3→glucan)        polymer is synthesized by a glucosyltransferase enzyme having        90% or greater identity to Gtf J.        22. The method of any one of embodiments 20 or 21 wherein the        substrate is paper or a polymer.        23. The method of any one of embodiments 20, 21 or 22 wherein        the aqueous coating composition further comprises:    -   iv) an additive.        24. The method of any one of embodiments 20, 21, 22 or 23        wherein the applied layer of coating composition, after having        at least a portion of the water removed, forms a surface having        an average porosity in the range of from 0.10 to 0.50        milliliters/gram.

EXAMPLES

Unless otherwise noted, all ingredients are available fromSigma-Aldrich, St. Louis, Mo.

Silica #1, having a pore volume of 1.8 ml/g and Silica # 2, amorphoussilica, having a pore volume of 1.2 ml/g are both available from the PQCorporation, Valley Forge, Pa.

PVOH #1, partially saponified PVOH, PVOH #2, silanol-modified PVOH andPVOH #3 polyvinyl alcohol are available from Kuraray Europe GmbH,Germany.

PVAc, vinyl acetate emulsion and Aminomethacrylate-based quaternarycopolymer are both available from Indulor Chemie GmbH, Germany.

HYDROCARB® 60 and HYDROCARB® 90 calcium carbonates are available fromOmya Incorporated, Proctor, Vt.

Calcium Silicate is available from Cirkel GmbH & Co, Haltern, Germany.

The water insoluble α-(1,3→glucan) polymer was produced according to amethod of U.S. Pat. No. 8,871,474. The polymer had a number averagedegree of polymerization of about 300 and >98% α-1,3 glycosidiclinkages.

SURFYNOL® 465 nonionic surfactant and other nonionic organic wettingagents are available from Air Products, Allentown, Pa.

Corn dextrin is available from Cargill, Wayzata, Minn.

PROXEL® GXL antimicrobial is available from Arch Chemicals, Inc.,Smyrna, Ga.

Pore Size Volume was measured using a POREMASTER® GT pore size analyzer,available from Quantachrome Instruments, Boynton Beach, Fla.

Coating Compositions 1-4

Coating compositions 1-4 were produced by dispersing compositions inwater according to the Table 1. The amounts in Table 1 are parts byweight.

TABLE 1 Coating Composition 1 2 3 4 Silica #1 75 50 65 50 Silica #2 5 1818 18 α-(1,3→glucan) polymer 13 25 10 25 Dispersing agent 7 7 7 7 PVOH#1 13 13 13 13 PVOH #2 21 21 21 21 PVAc 50 50 50 40 quaternary copoly.5.9 5.9 5.9 5.9 CaCl₂ 4.1 4.1 4.1 4.1

Coating Compositions 5, 6, 7 and Comparative Coating Compositions A andB

Coating compositions 5, 6, and 7 and Comparative coating compositions Aand B were also prepared by dispersing the ingredients of Table 2 inwater. The amounts in Table 2 are parts by weight.

TABLE 2 Coating Compositions Ingredient 5 6 A 7 B α-(1,3→glucan) polymer15 7 0 30 0 PVOH #3 0 15 15 0 0 HC 60 70 93 70 0 0 HC 90 0 0 0 70 100Calcium Silicate 15 0 30 0 0 Nonionic wetting agent 0 0.1 0.1 0 0 corndextrin 0 0 0 15 15

The aqueous coating compositions of Table 1 and 2 were applied to inkjet paper and dried. The dried coatings were then fed through an ink jetprinter printing a 600 dots per inch (dpi), 900 dpi, and 1200 dpi tovisually analyze the print quality using a rating scale of A, B, C, D,or F with A being the highest visual quality and F being the lowestvisual quality. In a second test, 1.7 seconds after the ink was appliedto the coating composition, the ink was wiped and the wiped area wasvisually analyzed and given a rating of A, B, C, D or F, with A beingthe best rating and F being the worst rating (i.e., the most smudged).In Table 3, a rating of a “u” means that the smudge rendered the inkunidentifiable. The results are shown in Table 3. The abbreviation “n/a”means not analyzed.

TABLE 3 Coating Composition 1 2 3 4 A 5 6 B 7 Coating  6.7  5.7  6.5 6.2 7.0  7.1  7.1 8.1  8.3  weight (g/m²) Coating 17.9 19.1 18.2 19.12.9  5.7  6.4 5.4  7.0  thickness (μm) Pore Size n/a n/a n/a n/a 0.440.28 n/a 0.28 0.18 Volume (ml/g) Non- A A A A A A A A A wiped rating(600 dpi) Wiped A A A A A A A F A rating (600 dpi) Non- A A A A A A A AA wiped rating (900 dpi) Wiped A D B A B A B u C rating (900 dpi) Non- AA A A A A C A B wiped rating (1200 dpi) Wiped F F F F F C F u F rating(1200 dpi)

Preparation of Coating Composition 8

A dispersion comprising 3 parts by weight (pbw) of the water insolubleα-(1,3→glucan) polymer, 5 pbw 1,2-propanediol, 1 pbw triethylene glycolbutyl ether, 10 pbw glycerol, 3 pbw 2-pyrrolidone, 0.15 pbw PROXEL® GXLantimicrobial, 0.5 pbw SURFYNOL® surfactant and 1 pbw polyurethane wasmixed with 76.35 pbw water.

A dispersion of aqueous Coating Composition 8 was applied to atransparency sheet and the coating was dried. The coated transparencysheet was placed in an ink jet printer and printed using color ink. As acomparison, an uncoated transparency sheet was also printed with thesame image. The coated transparency sheet showed sharp images and noevidence of mottling. In comparison, the uncoated transparency sheetshowed an unacceptable degree of bleeding and mottling.

Preparation of Coating Compositions 9 and 10, and Comparative CoatingComposition C

The following examples show coating performance for Folding Box Boards(FBB) and Label applications where coating compositions comprising waterinsoluble α-(1,3→glucan) polymer were formulated to improving printingperformance while preserving other key paper parameters such asbrightness and opacity.

Coating compositions 9 and 10 and Comparative Coating Composition C(Comp. C) were prepared by dispersing the ingredients of Table 4 inwater. The amounts in Table 4 are parts by weight. These coatingcompositions were coated onto Folding Box Boards.

TABLE 4 Coating Composition Ingredient Comp. C 9 10 Pigment Hydroplex 90carbonate 35 35 35 Hydroplex 60 carbonate 65 60 60 α-(1,3→glucan)polymer 0 5 10 Binder Litex 9740 (styrol butadiene latex) 12 12 12Mowiol 4-88 (11%-Lösung) 0.5 0.5 0.5 Property Viscosity (mPas) 450 450450 Solids Content (%) 45 45 45 Coating Weight (g/m²) 10.9 11.8 12.4

Coating procedure: All coating was performed on Sumet coating unit inblade coating mode with bent blade. Blade angle was 25°, Blade pressurewas 25 N, Roll pressure was 25 N and machine speed was 20 m/min.

Bristow wheel method and High speed fluid characterization: a definedvolume of ink is dispensed onto the substrate. It gives a track of theink which is longer if the setting speed is low. For inkjet applicationsit is important to have a track of shorter than 150 mm.

For the FBB-samples it is important to improve opacity of the coatingrelative to pure uncoated board and to improve printability relative toprecipitated calcium carbonate (PCC) coating. Whiteness was determinedonce with UV-component in the light source and once without.

The change in coating opacity when applying a standard varnish onto thesample was checked. The setting speed of ink on the coated samples wasprobed by means of Bristow wheel. Binding power of the coating was alsochecked by means of a pick test (ISO 3783). All coating compositionswere set to the same solids content (45%). To highlight the effect ofthe polysaccharide, the relative increase in whiteness (ISO 2470-1 and2470-2) for all the samples is shown. The results in Table 5 show thatthe polysaccharide is behaving quite similarly to calcium carbonatepigments. By exchanging pigment by polysaccharide one obtains the sameincrease in whiteness. To check the opacity of the coating further, athin film of standard varnish was applied from offset printing (ActegaTerrawet). Whiteness decreased by about 8 points for all samples. Hence,coating containing parts of polysaccharide have comparable brightnessproperties to other pigments. To determine the binding power of thecoating to the substrate we performed pick test, where medium viscosityoil was applied onto the surface and pulled with increasing speed.Higher values show a higher binding power to the substrate. The valuesin Table 5 indicate that coating adhesions were not affected by thepresence of polysaccharide.

Setting speed was tested by Bristow wheel method. The results in Table 5show that increasing the amount of polysaccharide in the coating gives adecrease in the track length and an increase in the setting speed. Theshorter track length compared to that of the reference sample(Comparative Coating Composition C) indicate that the use ofpolysaccharide yielded improved printability while preserving keycoating characteristics of whiteness and pick strength.

TABLE 5 Increase Increase Track Coating Coating Whiteness in inwhiteness length Pick Composition Description (g/m²) D 65 whiteness per10 g/m² (mm) Test Control Pure board — 42.24 — — — — Comp. C Controlwithout 10.9 57.13 11.88 10.90 112 2.59 polysaccharide 9  5 parts of11.8 57.95 12.70 10.76  99 2.47 polysaccharide 10 10 parts of 12.4 58.9713.72 11.06  92 2.82 polysaccharide

In Label application it is important to have a high opacity, even whenthe paper gets wet. Furthermore printability matters, so the settingbehavior of model ink at the coated samples was investigated. Thecomposition with polysaccharide (Coating Composition 11) was comparedwith compositions having three different TiO₂ controls (ComparativeCoating Compositions D, E, and F).

Coating composition 11 and Comparative Coating Compositions D, E, and F(Comp. D, Comp. E, and Comp. F) were prepared by dispersing theingredients of Table 6 in water. The amounts in Table 6 are parts byweight. These coating compositions were coated onto labels as describedabove.

TABLE 6 Coating Composition Ingredient Comp. D 11 Comp. E Comp. FPigment Hydroplex 90 carbonate 78 75 78 78 Hydragloss 90 clay 15 15 1515 TiO₂ (SR5 Slurry) 7 — — — TiO₂ Slurry Alternative A — — 7 — TiO₂Slurry Alternative B — — — 7 α-(1,3→glucan) polymer — 10 — — BinderLitex 9740 12 12 12 12 (styrol butadiene latex) Property Viscosity(mPas) 1000 1000 1000 1000 Solids Content (%) 45 45 45 45 Coating Weight(g/m²) 9.4 8.8 7.6 8.7

Table 7 shows the obtained data from whiteness and opacity measures. Thesubstrate contains optical brightening agent (OBA) which gives a highD65 whiteness. Since whiteness without UV part of the light ignores OBAand is comparable between all samples we have a direct measure for theopacity. The difference in D65 values. The data in Table 7 shows thatcoating formulations containing polysaccharide show comparable whiteness(ISO 2470-1 and 2470-2) and wet opacity (DIN 53146) as TiO₂-containingformulation. Moreover, the Bristow length measurement shows again thatformulations containing polysaccharide give the fastest setting speedand hence the shortest setting time (the shortest track length inBristow).

TABLE 7 Coating Coating Whiteness Whiteness 420 Opacity BristowComposition Description (g/m²) D65 (without OBA) wet length (mm) ControlUncoated 109.34 87.96 60.56 substrate Comp. D Reference 9.4  97.44 88.4371.54 134.6 TiO₂ 11 10 parts of 8.8 103.77 87.56 71.97 123  polysaccharide Comp. E Reference 7.6  99.92 88.46 70.75 149   TiO₂ Comp.F Reference 8.7  99.25 88.27 72.9  129.2 TiO₂

What is claimed is:
 1. A substrate, wherein at least a portion of thesubstrate is coated with a layer of a coating composition, the coatingcomposition comprising; i) water insoluble α-(1,3→glucan) polymer having90% or greater α-1,3-glycosidic linkages, less than 1% by weight ofα-1,3,6-glycosidic branch points and a number average degree ofpolymerization in the range of from 55 to 10,000; and ii) at least onepigment, at least one binder, or a combination thereof.
 2. The substrateof claim 1 wherein the substrate is a cellulose substrate, a polymer,paper, a textile, paperboard, cardboard, or corrugated board.
 3. Thesubstrate of claim 1, wherein the layer of coating composition comprisesan average pore size volume in the range of from 0.1 to 0.50milliliters/gram.
 4. The substrate of claim 1, wherein the binder ispolyvinyl alcohol, polyvinyl acetate, partially saponified polyvinylacetate, silanol-modified polyvinyl alcohol, polyurethane, starch, corndextrin, carboxy methyl cellulose, cellulose ethers, hydroxyethylcellulose, hydroxypropyl cellulose, ethylhydroxyethyl cellulose, methylcellulose, alginates, sodium alginate, xanthan, carrageenan, casein, soyprotein, guar gums, synthetic polymers, styrene butadiene latex, styreneacrylate latex, or a combination thereof.
 5. The substrate of claim 1,wherein the coating composition comprises in the range of from 0.1 to50% by weight of the water insoluble α-(1,3→glucan) polymer, based onthe total weight of the coating composition.
 6. The substrate of claim1, wherein the coating composition further comprises one or more of: iv)an additive.
 7. The substrate of claim 1, wherein the water insolubleα-(1,3→glucan) polymer is a linear polymer having greater than or equalto 99% of α-1,3-glycosidic linkages and less than 1% α-1,3,6-glycosidicbranch points.
 8. The substrate of claim 1, wherein the coatingcomposition is free from or essentially free from starch or hydroxyalkyl starch.
 9. The substrate of claim 6, wherein the additive is oneor more of a dispersant, a quaternary ammonium salts, calcium chloride,a surfactant, a hardener, a flowability improver, a lubricant, anantifoam, a releasing agent, a foaming agent, a penetrant, an opticalbrightener, a preservative, a biocide, a yellowing inhibitor, anultraviolet absorber, an antioxidant, an insolubiliser, an antistaticagent, a pH regulator, a water-resistance agent, a wet and/or drystrengthening agent, a cross-linking agent, a gloss-ink holdoutadditive, a grease and oil resistance additive, a leveling aid, or acombination thereof.
 10. An aqueous coating composition comprising thecoating composition of claim 1 and iii) an aqueous carrier.
 11. Theaqueous coating composition of claim 10, wherein the aqueous coatingcomposition is free from water soluble polysaccharides.
 12. The aqueouscoating composition of claim 10, wherein the aqueous carrier comprisesless than or equal to 60% by weight of the total weight of the aqueouscoating composition.
 13. The aqueous coating composition of claim 10,wherein the composition further comprises one or more of: iv) anadditive.
 14. The aqueous coating composition of claim 10, wherein thecomposition is essentially free from starch or hydroxyalkyl starch. 15.The aqueous coating composition of claim 10, wherein the α-(1,3→glucan)polymer is a linear polymer having greater than or equal to 99% ofα-1,3-glucosydic linkages and less than 1% α-1,3,6-branching points. 16.The aqueous coating composition of claim 10, wherein the binder ispolyvinyl alcohol, polyvinyl acetate, partially saponified polyvinylacetate, silanol-modified polyvinyl alcohol, polyurethane, starch, corndextrin, cellulose ethers, hydroxyethyl cellulose, hydroxypropylcellulose, ethylhydroxyethyl cellulose, methyl cellulose, alginates,sodium alginate, xanthan, carrageenan, guar gums, synthetic polymers,styrene butadiene latex or a combination thereof.
 17. The aqueouscoating composition of claim 13, wherein the additive is one or more ofa dispersant, a quaternary ammonium salts, calcium chloride, asurfactant, a hardener, a flowability improver, a lubricant, anantifoam, a releasing agent, a foaming agent, a penetrant, an opticalbrightener, a preservative, a biocide, a yellowing inhibitor, anultraviolet absorber, an antioxidant, an insolubiliser, an antistaticagent, a pH regulator, a water-resistance agent, a wet and/or drystrengthening agent, a cross-linking agent, a gloss-ink holdoutadditive, a grease and oil resistance additive, a leveling aid or acombination thereof.
 18. A method of forming a layer of a coatingcomposition on a substrate comprising: 1) applying an aqueous coatingcomposition to at least a portion of a substrate, wherein the aqueouscoating composition comprises; i) water insoluble α-(1,3→glucan) polymerhaving 90% or greater α-1,3-glycosidic linkages, less than 1% ofα-1,3,6-glycosidic branch points and a number average degree ofpolymerization in the range of from 55 to 10,000; ii) a pigment, abinder or a combination thereof; iii) an aqueous carrier; and 2)removing at least a portion of the aqueous carrier from the appliedlayer of the aqueous coating composition to form the layer of thecoating composition.
 19. The method of claim 18, wherein the substrateis paper or a polymer.